Article comprising tubular particles

ABSTRACT

An article has a density of from 0.03 to 0.45 g/cc. The article includes a plurality of anisotropic tubular particles that are randomly oriented in the article. The tubular particles include a thermoplastic elastomer foam and a non-foamed polymer disposed on an exterior surface of the thermoplastic elastomer foam as an outermost layer of the tubular particles. Each of the thermoplastic elastomer foam and the non-foamed polymer independently has a softening temperature determined according to DIN ISO 306. Moreover, the non-foamed polymer includes an additive that is responsive to non-heat energy to selectively heat the non-foamed polymer to its softening temperature prior to the thermoplastic elastomer foam reaching its softening temperature.

FIELD OF THE DISCLOSURE

The present disclosure generally relates to an article having aparticular density and including a plurality of anisotropic tubularparticles. More specifically, the tubular particles include athermoplastic elastomer foam and a non-foamed polymer disposed on anexterior surface of the thermoplastic elastomer foam as an outermostlayer of the particles. The non-foamed polymer includes an additive thatis responsive to non-heat energy to selectively heat the non-foamedpolymer.

BACKGROUND

Thermoplastic foam particles can be used to form a cushion-like materialby combining the particles loosely or binding them together to form aconnected network of particles. Binding of particles can be achieved byusing thermoset glues or using temperature and pressure along with theparticles' inherent thermoplastic (melting) behavior to fuse them to oneanother. During the binding process, particles are usually placed in amold under pressure to form an article. If using temperature to bind theparticles (e.g. by steam chest crack molding), the melting point of theparticles is usually approached/exceeded to enable fusion in the mold.Elevated temperatures coupled with pressure in the mold can have anunintended consequence of permanently distorting the particles whichleads to unwanted shrinkage of the article. Accordingly, there remainsopportunity for improvement.

SUMMARY OF THE DISCLOSURE

This disclosure provides an article having a density of from 0.03 to0.45 g/cc. The article includes a plurality of anisotropic tubularparticles that are randomly oriented in the article. The tubularparticles include a thermoplastic elastomer foam and a non-foamedpolymer disposed on an exterior surface of the thermoplastic elastomerfoam as an outermost layer of the tubular particles. Each of thethermoplastic elastomer foam and the non-foamed polymer independentlyhas a softening temperature determined according to DIN ISO 306.Moreover, the non-foamed polymer includes an additive that is responsiveto non-heat energy to selectively heat the non-foamed polymer to itssoftening temperature prior to the thermoplastic elastomer foam reachingits softening temperature.

This disclosure also provides a method of forming the article. Themethod includes the steps of providing the thermoplastic elastomer andthe non-foamed polymer, and co-extruding the thermoplastic elastomer andthe non-foamed polymer to form a tubular extrudate wherein thethermoplastic elastomer is foamed to form a thermoplastic elastomer foamduring co-extrusion and the non-foamed polymer is disposed on anexterior surface of the thermoplastic elastomer foam as an outermostlayer of the tubular extrudate. The method also includes the step ofsegmenting the tubular extrudate to form a plurality of anisotropictubular particles including the thermoplastic elastomer foam and thenon-foamed polymer disposed on the exterior of the thermoplasticelastomer foam as the outermost layer of the tubular particles. Themethod further includes the step of disposing the plurality ofanisotropic tubular particles in a mold and the step of applyingnon-heat energy to the plurality of anisotropic tubular particles toselectively heat the non-foamed polymer to its softening temperatureprior to the thermoplastic elastomer foam reaching its softeningtemperature and form the article such that the plurality of anisotropictubular particles are randomly oriented in the article.

BRIEF DESCRIPTION OF THE FIGURES

Other advantages of the present disclosure will be readily appreciated,as the same becomes better understood by reference to the followingdetailed description when considered in connection with the accompanyingdrawings wherein:

FIG. 1 is a side cross-sectional view of one embodiment of a particle ofthe instant disclosure;

FIG. 2 is a side cross-sectional view of another embodiment of aparticle of the instant disclosure;

FIG. 3 is a side cross-sectional view of one embodiment of an extrudateof the instant disclosure;

FIG. 4 is a side cross-sectional view of one embodiment of a pluralityof particles of the instant disclosure; and

FIG. 5 is a side cross-sectional view of one embodiment of the articleof the instant disclosure.

DETAILED DESCRIPTION OF THE PRESENT DISCLOSURE

This disclosure provides an article (10) having a density of from 0.03to 0.45 g/cc, e.g. as shown in FIG. 5. The article (10) itself is notparticularly limited in dimensions, size, or type. In variousembodiments, the article (10) is a shoe sole, a furniture cushion, anautomobile cushion, a mattress, a flooring surface, a flooringsubstrate, etc. In other embodiments, the density of the article (10) isfrom 0.03 to 0.4, from 0.05 to 0.4, from 0.1 to 0.35, from 0.15 to 0.3,from 0.2 to 0.25, from 0.03 to 0.1, from 0.03 to 0.25, from 0.03 to 0.2,from 0.03 to 0.15, from 0.03 to 0.05, from 0.04 to 0.09, from 0.05 to0.08, from 0.06 to 0.07, from 0.1 to 0.45, from 0.15 to 0.4, from 0.2 to0.35, or from 0.25 to 0.3, g/cc (or g/ml). The article (10) alsotypically has an ultimate breaking strength of from 0.1 to 4.0megapascal, from 0.4 to 3.0 megapascal, or from 0.5 to 1.5 megapascal,as determined using ASTM D 5035. In various additional non-limitingembodiments, all values and ranges of values between and including theaforementioned values are hereby expressly contemplated.

Anisotropic Tubular Particles:

The article (10) includes a plurality of anisotropic tubular particles(12), hereinafter described as “particles (12)”, e.g. as shown in FIG.4. The terminology “plurality” describes that the article (10) includesmultiple particles (12), i.e., three or more. The terminology“anisotropic” describes that the particles (12) exhibit physicalproperties that have different values when measured in differentdirections. For example, the particle may require a particular amount offorce to collapse the particle when that force is applied to the side ofthe particle. This required amount of force may be different whenapplied to the end of the particle to collapse the particle. Theparticles (12) are tubular and may be solid or hollow. In oneembodiment, the particles (12) are described as hollow cylinders. Inanother embodiment, the particles (12) are described as solid cylinders.

The cross-section of the particles (12) may be circular, oval, square,rectangular, or any other shape. In other words, the terminology“tubular” is not limited to circular or oval cross section. However, inthe Figures, the cross-sections are approximately circular. Theparticles (12) may be described as hollow or solid shapes having alength and a cross-section that may be any shape. In other embodiments,the particles (12) are curved/bent tubular shapes orbellowed/“accordion” shapes. Curving/bending the particles (12) canresult in different properties, as will bellowing the particles (12).The particles (12) may be alternatively described as pipes, conduits,tubes, cylinders, etc. The use of tubular particles typically allows forlower bulk density of the article to be achieved. Said differently, thegeometry of the particles typically allows for increased densityreduction, for example, relative to a comparative article that is formedwithout the technology of this disclosure.

The particles (12) are randomly oriented in the article (10), e.g. inthree dimensions. In other words, the particles (12) are not disposeduni-directionally or in any particular direction or directions in thearticle (10). The particles (12) are typically randomly oriented ordispersed in the article (10) in the x, y, and z dimensions. Typically,a cross-section of the article (10) would reveal no pattern to theorientation or dispersion of the particles (12) in the article (10).

The particles (12) are typically fused together but do not necessarilyhave to be “fused” so long as the article has the aforementioneddensity. In one embodiment, some of the particles (12) are fusedtogether and others are not. Typically, if fused, the particles (12) arefused using the method described below. The particles (12) may be fusedtogether at a plurality of points, e.g. along an edge of the particles(12) or along or across an exterior surface (26) of the particles (12).Alternatively, the particles (12) may be fused together at one or moreinterfaces of exterior layers of various particles (12). The particlesmay be melted together or otherwise adhered to one another, in any way,so long as the aforementioned density is achieved.

The particles (12) include a thermoplastic elastomer foam (14) and anon-foamed polymer (16) disposed on an exterior surface (26) of thethermoplastic elastomer foam (14) as an outermost layer (24) of theparticles (12). This non-foamed polymer (16) may be alternativelydescribed as an “exterior” non-foamed polymer (16). The terminology“outermost” or “exterior” may describe that one side of the layer isexposed to the environment and is not in contact with any other layer.In other words, an outermost layer is not sandwiched between any otherlayers.

The particles (12) may be, include, consist essentially of, or consistof, the thermoplastic elastomer foam (14) and the non-foamed polymer(16). The terminology “consists essentially of” describes that, invarious embodiments, the particles (12) are free of polymers that arenot the thermoplastic elastomer foam (14) or the non-foamed polymer (16)and may be free or, or may include, various polymer additives and/orprocessing additives known in the art.

Neither the thermoplastic elastomer foam (14) nor the non-foamed polymer(16) is particularly limited to any thickness, length, width, or heightin the particles (12). Typically, the thermoplastic elastomer foam (14)has a thickness of from 0.5 to 50, from 1 to 30, or from 1 to 10, mm inthe particles (12). Similarly, the non-foamed polymer (16) typically hasa thickness of from 0.001 to 10, from 0.005 to 5, or from 0.01 to 1, mmin the particles (12).

The particles (12) themselves are also not particularly limited to anythickness, length, width, or height. In various embodiments, theparticles (12) have a length from 1 to 50, from 1 to 40, or from 1.5 to30, mm. In other embodiments, the particles (12) have a diameter from 1to 100, from 1 to 50, or from 1 to 30, mm. In still other embodiments,the size of the particles (12) is designed such that they have diametersof about 0.5 mm to about 25 mm. The diameters of the particles (12) maybe about 2 mm to about 10 mm or about 3 mm to about 8 mm. In variousadditional non-limiting embodiments, all values and ranges of valuesbetween and including the aforementioned values are hereby expresslycontemplated.

Thermoplastic Elastomer Foam:

The thermoplastic elastomer foam (14) is not particularly limited solong as it is a foam. However, the thermoplastic elastomer foam (14) istypically formed from a thermoplastic elastomer that is not foamed. Inone embodiment, and as described below, the thermoplastic elastomer foam(14) is typically foamed during extrusion of a non-foamed thermoplasticelastomer. For example, a non-foamed thermoplastic elastomer may beprovided to an extruder (e.g. in pellet form) and then, during theprocess of extrusion, may be foamed to form the thermoplastic elastomerfoam (14). Additional process steps may also be useful such as addingexpandable microspheres, adding blowing agents, e.g. NaHCO₃ or citricacid, or adding gas, e.g. CO₂, N₂, or Ar, by injection into a melt.Combinations of these steps may also be used. As described below, theterminology “thermoplastic elastomer” and “thermoplastic elastomer foam(14)” may be used interchangeably in various non-limiting embodiments.

In various embodiments, the thermoplastic elastomer foam (14) isproduced using a non-foamed thermoplastic elastomer having a durometerfrom Shore 40A to 83D as determined using DIN ISO 7619-1. In variousembodiments, the non-foamed thermoplastic elastomer used to form thethermoplastic elastomer foam (14) has a durometer from 40A to 83D, from60A to 70D, or from 80A to 95A, as determined using DIN ISO 7619-1. Thethermoplastic elastomer foam (14) itself typically has a density from0.1 to 0.6, from 0.15 to 0.55, from 0.2 to 0.5, from 0.25 to 0.45, from0.3 to 0.4, from 0.3 to 0.35, or from 0.35 to 0.4, g/cc (or g/ml). Invarious additional non-limiting embodiments, all values and ranges ofvalues between and including the aforementioned values are herebyexpressly contemplated.

The thermoplastic elastomer and/or thermoplastic elastomer foam (14) maybe chosen from thermoplastic polyurethane elastomers (TPU),thermoplastic co-polyester elastomers (TPC), thermoplastic styrenicelastomers (TPS), thermoplastic polyamides (TPA), thermoplasticvulcanates (TPV), thermoplastic polyolefins (TPO), and combinationsthereof.

Thermoplastic Polyurethane Elastomers:

Thermoplastic polyurethane elastomers (e.g. foamed or non-foamed) mayalso be described herein simply as TPUs, thermoplastic polyurethanes, orTPE-U's. Thermoplastic polyurethane elastomers typically include linearsegmented polymeric blocks including hard and soft segments. Withoutintending to be bound by any particular theory, it is believed that thesoft segments are of low polarity and form an elastomer matrix whichprovides elastic properties to the thermoplastic polyurethane. The hardsegments are believed to be shorter than the soft segments, to be ofhigher polarity, and act as multifunctional tie points that functionboth as physical crosslinks and reinforcing fillers. The physicalcrosslinks are believed to disappear when heat is applied, thus allowingthe thermoplastic polyurethanes to be used in the variety of processingmethods.

The thermoplastic polyurethane may be further defined as a polyetherthermoplastic polyurethane, a polyester thermoplastic polyurethane, or acombination of a polyether thermoplastic polyurethane and a polyesterthermoplastic polyurethane. That is, the non-foamed and/or the foamedthermoplastic polyurethane may be further defined as including or beingthe reaction product of an isocyanate and a polyether polyol, apolyester polyol, an aliphatic or olefinic polyol or a combination ofthese polyols. Alternatively, the non-foamed and/or the foamedthermoplastic polyurethane may be further defined as a multi-blockcopolymer produced from a poly-addition reaction of an isocyanate with alinear polymeric glycol (e.g. having a weight average molecular weightof from 500 to 8,000 g/mol), low molecular weight diol (e.g. having aweight average molecular weight of from 50 to 600 g/mol), and or/polyol.Typically, non-foamed and/or foamed thermoplastic polyurethanes can beobtained by varying a ratio of hard segments and soft segments, asdescribed above. Physical properties such as shore Hardness, along withmodulus, load-bearing capacity (compressive stress), tear strength, andspecific gravity, typically increases as a ratio of hard segments tosoft segments increases. In various additional non-limiting embodiments,all values and ranges of values between and including the aforementionedvalues are hereby expressly contemplated.

In one embodiment, the non-foamed and/or the foamed thermoplasticpolyurethane is a polyester thermoplastic polyurethane and includes thereaction product of a polyester polyol, an isocyanate component, and achain extender. Suitable polyester polyols are typically produced from areaction of a dicarboxylic acid and a glycol having at least one primaryhydroxyl group. Suitable dicarboxylic acids include, but are not limitedto, adipic acid, methyl adipic acid, succinic acid, suberic acid,sebacic acid, oxalic acid, glutaric acid, pimelic acid, azelaic acid,phthalic acid, terephthalic acid, isophthalic acid, and combinationsthereof. Glycols that are suitable for use in producing the polyesterpolyols include, but are not limited to, ethylene glycol, butyleneglycol, hexanediol, bis(hydroxymethylcyclohexane), 1,4-butanediol,diethylene glycol, 2-methyl-propanediol, 3-methyl-pentanediol,2,2-dimethyl propylene glycol, 1,3-propylene glycol, and combinationsthereof.

In an alternative embodiment, the non-foamed and/or the foamedthermoplastic polyurethane is a polyester thermoplastic polyurethane andincludes the reaction product of a suitable chain extender, anisocyanate component, and a polymeric polyol. Suitable chain extendersinclude, but are not limited to, diols including ethylene glycol,propylene glycol, butylene glycol, 1,4-butanediol, butenediol,butynediol, 2-ethyl-1,3-hexanediol, xylylene glycols, amylene glycols,1,4-phenylene-bis-beta-hydroxy ethyl ether,1,3-phenylene-bis-beta-hydroxy ethyl ether,bis-(hydroxy-methyl-cyclohexane), hexanediol, and thiodiglycol, diaminesincluding ethylene diamine, propylene diamine, butylene diamine,hexamethylene diamine, cyclohexalene diamine, phenylene diamine,tolylene diamine, xylylene diamine, 3,3′-dichlorobenzidine, 3,3′- anddinitrobenzidine, alkanol amines including ethanol amine, aminopropylalcohol, 2,2-dimethyl propanol amine, 3-aminocyclohexyl alcohol, andp-aminobenzyl alcohol, and combinations thereof. Specific examples ofsuitable polyester thermoplastic polyurethanes that can be used in thisinvention include, but are not limited to, Elastollan® 600, 800, B, C,and S Series polyester thermoplastic polyurethanes commerciallyavailable from BASF Corporation.

In a further embodiment, the non-foamed and/or the foamed thermoplasticpolyurethane is a polyether thermoplastic polyurethane and includes thereaction product of a polyether polyol, an isocyanate component, and achain extender. Suitable polyether polyols include, but are not limitedto, polytetramethylene glycol, polyethylene glycol, polypropyleneglycol, and combinations thereof. In yet another embodiment, thenon-foamed and/or the foamed thermoplastic polyurethane is a polyetherthermoplastic polyurethane and includes the reaction product of a chainextender and an isocyanate component. It is to be understood that anychain extender known in the art can be used by one of skill in the artdepending on the desired properties of the thermoplastic polyurethane.Specific examples of suitable polyether thermoplastic polyurethanes thatmay be used in this invention include, but are not limited to,Elastollan® 1000, 1100 and 1200 Series polyether thermoplasticpolyurethanes commercially available from BASF Corporation.

In a further embodiment, the non-foamed and/or the foamed thermoplasticpolyurethane is an aliphatic or olefinic thermoplastic polyurethane andincludes the reaction product of an aliphatic or olefinic thermoplasticpolyol, an isocyanate component and a chain extender. Suitable polyetherpolyols include, but are not limited to, hydrogenated polybutadiene ornon-hydrogenated polybutadiene and combinations thereof or incombination with polyester and/or polyether polyol. It is to beunderstood that any chain extender known in the art can be used by oneof skill in the art depending on the desired properties of thethermoplastic polyurethane.

Typically, the polyether, polyester, aliphatic or olefinic polyols usedto form the non-foamed and/or the foamed thermoplastic polyurethane havea weight average molecular weight of from 600 to 3,000 g/mol. However,the polyols are not limited to this molecular weight range. In oneembodiment, starting materials used to form the non-foamed and/or thefoamed thermoplastic polyurethane (e.g., a linear polymeric glycol, alow molecular weight diol, and/or a polyol) have average functionalitiesof approximately 2. For example, any pre-polymer or monomer can have 2terminal reactive groups to promote formation of high molecular weightlinear chains with no or few branch points in the non-foamed and/or thefoamed thermoplastic polyurethane. In various additional non-limitingembodiments, all values and ranges of values between and including theaforementioned values are hereby expressly contemplated.

The isocyanate component that is used to form the non-foamed and/or thefoamed thermoplastic polyurethane typically includes, but is not limitedto, isocyanates, diisocyanates, polyisocyanates, and combinationsthereof. In one embodiment, the isocyanate component includes ann-functional isocyanate. In this embodiment, n is a number typicallyfrom 2 to 5, more typically from 2 to 4, still more typically of from 2to 3, and most typically about 2. It is to be understood that n may bean integer or may have intermediate values from 2 to 5. The isocyanatecomponent typically includes an isocyanate selected from the group ofaromatic isocyanates, aliphatic isocyanates, and combinations thereof.In another embodiment, the isocyanate component includes an aliphaticisocyanate such as hexamethylene diisocyanate (HDI),dicyclohexyl-methyl-diisocyanate (H12MDI), isophoron-diisocyanate, andcombinations thereof. If the isocyanate component includes an aliphaticisocyanate, the isocyanate component may also include a modifiedmultivalent aliphatic isocyanate, i.e., a product which is obtainedthrough chemical reactions of aliphatic diisocyanates and/or aliphaticpolyisocyanates. Examples include, but are not limited to, ureas,biurets, allophanates, carbodiimides, uretonimines, isocyanurates,urethane groups, dimers, trimers, and combinations thereof. Theisocyanate component may also include, but is not limited to, modifieddiisocyanates employed individually or in reaction products withpolyoxyalkyleneglycols, diethylene glycols, dipropylene glycols,polyoxyethylene glycols, polyoxypropylene glycols,polyoxypropylenepolyoxethylene glycols, polyesterols, polycaprolactones,and combinations thereof.

Alternatively, the isocyanate component can include an aromaticisocyanate. If the isocyanate component includes an aromatic isocyanate,the aromatic isocyanate typically corresponds to the formula R′(NCO)_(z)wherein R′ is aromatic and z is an integer that corresponds to thevalence of R′. Typically, z is at least two. Suitable examples ofaromatic isocyanates include, but are not limited to,tetramethylxylylene diisocyanate (TMXDI), 1,4-diisocyanatobenzene,1,3-diisocyanato-o-xylene, 1,3-diisocyanato-p-xylene,1,3-diisocyanato-m-xylene, 2,4-diisocyanato-1-chlorobenzene,2,4-diisocyanato-1-nitro-benzene, 2,5-diisocyanato-1-nitrobenzene,m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-toluenediisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluenediisocyanate, 1,5-naphthalene diisocyanate, 1-methoxy-2,4-phenylenediisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethanediisocyanate, 4,4′-biphenylene diisocyanate,3,3′-dimethyl-4,4′-diphenylmethane diisocyanate,3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, triisocyanates such as4,4′,4″-triphenylmethane triisocyanate polymethylene polyphenylenepolyisocyanate and 2,4,6-toluene triisocyanate, tetraisocyanates such as4,4′-dimethyl-2,2′-5,5′-diphenylmethane tetraisocyanate, toluenediisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethanediisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylenepolyphenylene polyisocyanate, corresponding isomeric mixtures thereof,and combinations thereof. Alternatively, the aromatic isocyanate mayinclude a triisocyanate product of m-TMXDI and 1,1,1-trimethylolpropane,a reaction product of toluene diisocyanate and 1,1,1-trimethylolpropane,and combinations thereof. In one embodiment, the isocyanate componentincludes a diisocyanate selected from the group of methylene diphenyldiisocyanates, toluene diisocyanates, hexamethylene diisocyanates,H12MDIs, and combinations thereof. The isocyanate component can alsoreact with the polyol and/or chain extender in any amount, as determinedby one skilled in the art.

Thermoplastic Polyester Elastomers:

The thermoplastic elastomer foam may alternatively be a thermoplasticpolyester elastomer, also known as a TPC. Thermoplastic elastomers aremay also be described as thermoplastic rubbers and are typically a classof copolymers or a physical mix of polymers (e.g. a plastic and arubber) which have both thermoplastic and elastomeric properties.Non-limiting examples of thermoplastic polyester elastomers are Amitelfrom DSM and Hytrel from DuPont.

Thermoplastic Styrenic Elastomers:

The thermoplastic elastomer (foam) may alternatively be a thermoplasticstyrenic elastomer, also known as a styrol, styrenic block copolymerwith ethylene, propylene, butadiene, isoprene units, or a TPS.Thermoplastic styrenic elastomers are typically based on A-B-A typeblock structure where A is a hard phase and B is an elastomer.Non-limiting examples of thermoplastic styrenic elastomers are Kraton Dand Kraton G.

Thermoplastic Vulcanizate Elastomers:

The thermoplastic elastomer (foam) may alternatively be a thermoplasticvulcanate elastomer, also known as a TPV. A non-limiting example of athermoplastic vulcanate elastomer is Santoprene from ExxonMobil.

Thermoplastic Polyamide Elastomers:

The thermoplastic elastomer (foam) may alternatively be a thermoplasticpolyamide elastomer, also known as a TPA. A non-limiting example of athermoplastic polyamide elastomer is Vestamid E from Evonik.

Thermoplastic Polyolefin Elastomers:

The thermoplastic elastomer (foam) may alternatively be a thermoplasticpolyolefin elastomer, also known as a TPO. A non-limiting example of athermoplastic polyolefin elastomer is Engage from Dow.

Non-Foamed Polymer:

Referring back to the non-foamed polymer (16) itself, the non-foamedpolymer (16) is disposed on an exterior surface (26) of thethermoplastic elastomer foam (14) as the outermost layer (24) of theparticles (12). The non-foamed polymer (16) may be disposed on, and indirect contact with, the exterior surface (26) of the thermoplasticelastomer foam (14), e.g. as set forth in FIG. 1, or may be disposed on,and spaced apart from, the exterior surface (26) of the thermoplasticelastomer foam (14), as set forth in FIG. 2. A single non-foamed polymer(16) may be used or a combination of polymers may be used. In oneembodiment, the thermoplastic elastomer foam (14) and the non-foamedpolymer (16) are chemically identical. In another embodiment, thethermoplastic elastomer foam (14) and the non-foamed polymer (16) arechemically different.

The non-foamed polymer (16) is not particularly limited. The non-foamedpolymer (16) may be, include, consist essentially of, or consist of apolymer chosen from polyurethanes (foamed or non-foamed), thermoplasticelastomers (foamed or non-foamed), polyalkylenes, such as polyethylenes,polypropylenes, polyalkylene naphthalates and terephthalates,polyimides, polyamides, polyetherimides, polystyrenes, acrylonitriles,polycarbonates, polyalkylacrylates, polyacrylates, derivatives ofcellulose, halogenated polymers, polysulfones, polyethersulfones,polyacrylonitrile, silicones, epoxies, polyvinylacetates,polyether-amides, ionomeric resins, elastomers, styrene-butadienecopolymers, styrene-acrylonitrile copolymer, polyesters, polyolefins,polystyrenes, isomers thereof, copolymers thereof, and combinationsthereof. In various embodiments, the non-foamed polymer (16) is chosenfrom Elastollan 880A13N, Elastollan ER368511, and combinations thereof.In other embodiments, the non-foamed polymer (16) is chosen fromunfoamed thermoplastic elastomers (different from any described above),unfoamed thermoplastic elastomers such as TPS, TPV, TPO, and TPA, andcombinations thereof.

In various embodiments, the thermoplastic elastomer foam (14) may beformed utilizing one or more of the aforementioned polymers, e.g. inamount of up to about 50 weight percent of the polymers. In variousembodiments, the thermoplastic elastomer foam (14) is formed using 1, 2,3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50, weight percent of one ormore of the aforementioned polymers with the balance being thethermoplastic elastomer. In various additional non-limiting embodiments,all values and ranges of values between and including the aforementionedvalues are hereby expressly contemplated.

Softening Temperature:

Each of the thermoplastic elastomer foam (14) and the non-foamed polymer(16) independently has a softening temperature determined according toASTM DIN ISO 306. In various embodiments, the softening temperature ofthe non-foamed polymer (16) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, or more C,higher or lower than the softening temperature of the thermoplasticelastomer foam (14). The softening temperature of the thermoplasticelastomer foam (14) and the non-foamed polymer (16) may be the same.Without intending to be limited by any particular theory, it is believedthat a lower softening temperature of the polymer allows the particlesto be heated to this lower softening temperature, thereby softening orplasticizing the polymer and allowing the polymer to become sticky,thereby adhering particles together. In some embodiments, since thesoftening temperature of the polymer is lower than the softeningtemperature of the thermoplastic elastomer foam (14), the thermoplasticelastomer foam (14) itself does not melt/soften and thereby can retainits properties and dimensions. This typically results in an article thatdoes not suffer from shrinkage after removal from the mold along withdensification i.e., an unwanted increase in density due tocompaction/consolidation/agglomeration of the thermoplastic elastomerfoam (14) in the particles themselves. In other embodiments, thepresence of the additive, described in greater detail below, allows thenon-foamed polymer (16) to be preferentially heated to its softeningtemperature before the thermoplastic elastomer foam (14) reaches itssoftening temperature. This can occur in various embodiments no matterwhether the softening temperature of the non-foamed polymer (16) isbelow, equal to, or above, the softening temperature of thethermoplastic elastomer foam (14). In various additional non-limitingembodiments, all values and ranges of values between and including theaforementioned values are hereby expressly contemplated.

In various embodiments, the softening temperature of the non-foamedpolymer (16) is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50, oreven more, C lower than the softening temperature of the thermoplasticelastomer foam (14). In still other embodiments, the softeningtemperature of the non-foamed polymer (16) is from 5 to 20, from 10 to20, from 15 to 50, from 20 to 45, from 25 to 40, from 30 to 35, from 15to 30, from 15 to 25, or from 15 to 20, C higher or lower than thesoftening temperature of the thermoplastic elastomer foam (14). Invarious embodiments, the softening temperature of the thermoplasticelastomer foam (14) is from 40 to 180, from 80 to 180, from 90 to 160,from 100 to 160, or from 110 to 150, C. In other embodiments, thesoftening temperature of the non-foamed polymer (16) is from 40 to 180,from 40 to 120, from 50 to 100, from 60 to 80, from 60 to 70, from 60 to65, or from 60 to 70, C. Differences in melting or softening points ofthe thermoplastic elastomer and the polymer, either as part of theparticles individually, or even if measured after the article is formed,may be detected by various analytical procedures, such as by using DSCinstrumentation and procedures. In various additional non-limitingembodiments, all values and ranges of values between and including theaforementioned values are hereby expressly contemplated.

Additive:

The non-foamed polymer (16) includes an additive that is responsive tonon-heat energy to selectively heat the non-foamed polymer (16) to itssoftening temperature prior to the thermoplastic elastomer foam (14)reaching its softening temperature. In other words, the additive may beresponsive to various types of energy that are not (directly) heat. Forexample, these energies may be microwave energy, radio frequency energy,laser energy, infrared energy, ultraviolet energy, x-ray energy, e-beamenergy, electromagnetic energy, magnetic energy, electrical energy, andcombinations thereof. Although each of these energies may heat thenon-foamed polymer (16) and/or the thermoplastic elastomer foam (14),these energies are not considered to be “heat” in and of themselves.Therefore, the terminology “non-heat energy” typically refers to energythat is not conduction or convection.

In various embodiments, it may be said that the additive is responsiveto radiation, e.g. electromagnetic radiation, to selectively heat thenon-foamed polymer (16) to its softening temperature prior to thethermoplastic elastomer foam (14) reaching its softening temperature. Instill other embodiments, it may be said that the additive is responsiveto dielectric heating to selectively heat the non-foamed polymer (16) toits softening temperature prior to the thermoplastic elastomer foam (14)reaching its softening temperature. Dielectric heating, also known aselectronic heating, RF heating, and high-frequency heating, is theprocess in which a high-frequency alternating electric field, or radiowave or microwave electromagnetic radiation heats a (dielectric)material. At higher frequencies, this heating is caused by moleculardipole rotation within the (dielectric) material.

Dielectric heating may be based on molecular rotation in materialsincluding polar molecules having an electrical dipole moment, with theconsequence that they will align themselves in an electromagnetic field.If the field is oscillating, as it is in an electromagnetic wave or in arapidly oscillating electric field, these molecules rotate continuouslyby aligning with it. This is called dipole rotation, or dipolarpolarization. As the field alternates, the molecules reverse direction.Rotating molecules push, pull, and collide with other molecules (throughelectrical forces), distributing the energy to adjacent molecules andatoms in the material. Once distributed, this energy appears as heat.

Temperature is related to the average kinetic energy (energy of motion)of the atoms or molecules in a material, so agitating the molecules inthis way increases the temperature of the material. Thus, dipolerotation is a mechanism by which energy in the form of electromagneticradiation can raise the temperature of an object.

Dipole rotation is the mechanism normally referred to as dielectricheating, and is most widely observable in a microwave apparatus.Dielectric heating involves the heating of electrically insulatingmaterials by dielectric loss. A changing electric field across thematerial causes energy to be dissipated as the molecules attempt to lineup with the continuously changing electric field. This changing electricfield may be caused by an electromagnetic wave propagating in free space(as in a microwave apparatus), or it may be caused by a rapidlyalternating electric field inside a capacitor. In the latter case, thereis no freely-propagating electromagnetic wave, and the changing electricfield may be seen as analogous to the electric component of an antennanear field. In this case, although the heating is accomplished bychanging the electric field inside the capacitive cavity atradio-frequency (RF) frequencies, no actual radio waves are eithergenerated or absorbed. In this sense, the effect is the directelectrical analog of magnetic induction heating, which is alsonear-field effect (thus not involving radio waves).

Frequencies from 10-100 MHz are typically necessary to cause efficientdielectric heating, although higher frequencies can work equally well orbetter, and in some materials lower frequencies also have significantheating effects. Dielectric heating at low frequencies, as a near-fieldeffect, typically requires a distance from electromagnetic radiator toabsorber of less than ½π≈⅙ of a wavelength. It is thus a contact processor near-contact process, since it usually sandwiches the material to beheated between metal plates taking the place of the dielectric in whatis effectively a very large capacitor. However, actual electricalcontact is not necessary for heating a dielectric inside a capacitor, asthe electric fields that form inside a capacitor subjected to a voltagedo not require electrical contact of the capacitor plates with the(non-conducting) dielectric material between the plates. Because lowerfrequency electrical fields penetrate non-conductive materials moredeeply than do microwaves, it can be used to rapidly heat and preparepolymers so long as they fit between the capacitor plates. In variousadditional non-limiting embodiments, all values and ranges of valuesbetween and including the aforementioned values are hereby expresslycontemplated.

At very high frequencies, the wavelength of the electromagnetic fieldbecomes shorter than the distance between the metal walls of the heatingcavity, or than the dimensions of the walls themselves. This istypically the case inside a microwave apparatus. In such cases,conventional far-field electromagnetic waves form (the cavity no longeracts as a pure capacitor, but rather as an antenna), and are absorbed tocause heating, but the dipole-rotation mechanism of heat depositionremains the same. However, microwaves are not efficient at causing theheating effects of low frequency fields that depend on slower molecularmotion, such as those caused by ion-drag.

In various embodiments, the additive is one or more of the following butis not limited to the following:

Dielectric Dielectric Conductive Conductivity Conductive ConductivityMaterials Constant Materials (S/cm) Materials (S/cm) Graphite 15 Carbon1.00 × 10⁸ Platinum 9.43 × 10⁶ (Graphene) Zirconium 28 Silver 6.30 × 10⁷Tin 9.17 × 10⁶ Oxide Tantalum 50 Copper 5.96 × 10⁷ Carbon 6.99 × 10⁶Pentoxide Steel Water 88 Annealed 5.80 × 10⁷ Lead 4.55 × 10⁶ CopperTitanium 173 Gold 4.10 × 10⁷ Titanium 2.38 × 10⁶ Oxide Strontium 230Aluminum 3.50 × 10⁷ Grain 2.17 × 10⁶ Titanate Oriented Oxide ElectricalSteel Strontium 310 Calcium 2.98 × 10⁷ Manganin 2.07 × 10⁶ TitanateBarium 800 Tungsten 1.79 × 10⁷ Constantan 2.04 × 10⁶ Strontium TitanateLead 6000 Zinc 1.69 × 10⁷ Stainless 1.45 × 10⁶ Zirconium Steel TitanateBarium 10000 Nickel 1.43 × 10⁷ Mercury 1.02 × 10⁶ Titanate Conjugated100000 Lithium 1.08 × 10⁷ Nichrome  6.7 × 10⁵ Polymers Calcium 250000Iron 1.00 × 10⁷ GaAs   1 × 10³ Copper Titanate

Conductive Materials Conductivity (S/cm) Carbon (Amorphous)   2 × 10³Carbon (Graphite) 3.00 × 10⁵  PEDOT:PSS 4.6 × 10³

In various embodiments, the additive is chosen from dielectric materialshaving a dielectric constant between or including one or more of theaforementioned dielectric constants. In other embodiments, the additiveis chosen from conductive materials having a conductivity between orincluding one or more of the conductivity values set forth above. Invarious non-limiting embodiments, all materials within theaforementioned ranges of dielectric constants and conductivity valuesare hereby expressly contemplated. In various additional non-limitingembodiments, all values and ranges of values between and including theaforementioned values are hereby expressly contemplated.

In other embodiments, the additive is chosen from barium, titanate,aluminum, carbon, and combinations thereof. Also, the additive is nottypically limited in amount. In various embodiments, the additive ispresent in the non-foamed polymer (16) in an amount of from 0.01 to 10,from 0.01 to 0.1, from 0.1 to 1, from 1 to 10, from 0.05 to 0.1, from0.1 to 0.5, from 0.5 to 1, from 5 to 10, etc, weight percent based on atotal weight of the non-foamed polymer (16). In various additionalnon-limiting embodiments, all values and ranges of values between andincluding the aforementioned values are hereby expressly contemplated.

Additional Polymers:

In various embodiments, the article (10) and/or particles (12) alsoincludes an intermediate polymer (18), e.g. disposed between the“exterior” non-foamed polymer (16) (i.e., the polymer disposed on theexterior surface (26) of the thermoplastic elastomer as the outermostlayer (24) of the particles (12)) and the thermoplastic elastomer foam(14), e.g. as set forth in FIG. 2. This intermediate polymer (18) may besandwiched between the exterior non-foamed polymer (16) and thethermoplastic elastomer foam (14). The intermediate polymer (18) may bedisposed on and in direct contact with the thermoplastic elastomer foam(14) and/or the exterior non-foamed polymer (16). Alternatively, theintermediate polymer (18) may be disposed on, but spaced apart from, thethermoplastic elastomer foam (14) and/or the exterior non-foamed polymer(16) (not shown in the Figures).

In other embodiments, the article (10) and/or particles (12) includes aninterior polymer (20) that may be disposed on and in direct contact withthe thermoplastic elastomer foam (14) such that the thermoplasticelastomer foam (14) is disposed between the interior polymer (20) andthe exterior non-foamed polymer (16), e.g. as shown in FIG. 2. In thisembodiment, the thermoplastic elastomer foam (14) is typicallysandwiched between the interior polymer (20) and the exterior non-foamedpolymer (16). In another embodiment, the intermediate polymer (18) mayalso be present and be disposed in any position between the interiorpolymer (20) and the exterior non-foamed polymer (16). For example, theinterior polymer (20) may be disposed on and in direct contact with thethermoplastic elastomer foam (14) and/or the exterior non-foamed polymer(16). Alternatively, the interior polymer (20) may be disposed on, butspaced apart from, the thermoplastic elastomer foam (14) and/or theexterior non-foamed polymer (16). It is contemplated that one or moreintermediate polymers (18) may be utilized and one or more interiorpolymers (20) may be utilized. It is contemplated that the interiorpolymer (20) may be disposed as an innermost layer of the particles (12)such that the interior polymer (20) is exposed to a hollow portion ofthe particles (12) as shown in FIG. 2 and not sandwiched between anylayers. For example, the interior polymer (20) may only be in contactwith another polymer (e.g. the thermoplastic elastomer foam (14)) on oneside. In another example, the interior polymer (20) defines an interiorsurface of the particles (12).

Any one or more of the intermediate polymer (18) and/or the interiorpolymer (20) may be as described above relative to the exteriornon-foamed polymer (16) or different. The intermediate polymer (18), theinterior polymer (20), and/or the exterior non-foamed polymer (16) mayall be the same or different from one another. In various embodiments,the interior polymer (20) is chosen from thermoplastic urethane (TPU),polyamide-6, and thermoplastic amide (TPA). In other embodiments, theintermediate polymer (18) is chosen from thermoplastic urethane (TPU),polyamide-6 (PA6), and thermoplastic amide (TPA).

Method of Forming the Article:

This disclosure also provides a method of forming the article (10). Themethod includes the step of providing the (non-foamed) thermoplasticelastomer and the aforementioned non-foamed polymer, as described above.The method also includes the step of co-extruding the (non-foamed)thermoplastic elastomer and the exterior non-foamed polymer (16) to forma tubular extrudate (22) (e.g. as set forth in FIG. 3) wherein the(non-foamed) thermoplastic elastomer is foamed during co-extrusion(thereby forming the thermoplastic elastomer foam (14)) and the exteriornon-foamed polymer (16) is disposed on the thermoplastic elastomer foam(14) as an outermost layer (28) of the tubular extrudate (22). The stepof co-extruding is not particularly limited and may be as known in theart. Said differently, the step of co-extruding may include one or moresub-steps, temperatures, conditions, etc., that are known in the art.For example, in various embodiments, the step of co-extruding utilizesthe following parameters which may be modified as understood by those ofskill in the art:

Die Type: Crosshead; extruder 1 (1½″ dia.); Zone 1—340 F; Zone 2—360 F;Zone 3—370 F;Zone 4—370 F; Clamp—370 F; Adapter—370 F; Head Pressure—4000 psi; ScrewRPM—12.5, Screw Torque—18.5%; Extruder 2 (¾″ dia.); Zone 1—275 F; Zone2—320 F; Zone 3—340 F; Clamp—340 F; Adapter—340 F; Head Pressure—3800psi; Screw RPM—15; Screw Torque—31.6%; Die Head—370 F; Die—370 F; TakeOff Motor 230 RPM; Rate Indicator 21.3. Alternatively, one or moreparameters of co-extrusion may be as described in the Examples. Invarious additional non-limiting embodiments, all values and ranges ofvalues between and including the aforementioned values are herebyexpressly contemplated.

The method also includes the step of segmenting the tubular extrudate(22) to form the plurality of the particles (12). The step of segmentingis typically further defined as cutting or chopping but is notparticularly limited.

The method further includes the step of disposing the plurality ofparticles (12) in a mold. The particles (12) are typically disposed inthe mold in a random fashion, e.g. poured in. This typically allows forthe random or three-dimensional orientation of the particles (12) in thefinal product. In various embodiments, the particles (12) are either (1)poured manually “by hand” into a mold, or (2) injected into a mold usingan air conveyance system. Typically, the mold is filled while in an openposition, allowing particles to “overfill” the mold. After the mold isclosed, the particles are typically forced together which promotes moresurface area contact. This is intended to promote increased adhesion.

The method also includes applying non-heat energy to the plurality ofanisotropic tubular particles to selectively heat the non-foamed polymerto its softening temperature prior to the thermoplastic elastomer foamreaching its softening temperature and form the article such that theplurality of anisotropic tubular particles are randomly oriented in thearticle. Any of the energies or frequencies described above may be usedin the method.

The method may alternatively also include the step of heating theplurality of particles (12) to form the article (10), e.g. such that theplurality of particles (12) are randomly oriented in the article (10).The step of heating is not particularly limited and may include heatingby electricity, gas, steam, etc. In one embodiment, the step of heatingis further defined as heating the particles (12) and/or the mold itselfwith steam, e.g. as in a steam chest crack molding process. In anotherembodiment, the step of heating (and/or the entire method) may befurther defined as a steam chest crack molding process. The particularsteps may be as known in the art and/or as described above. The step ofheating may occur before, during, or after, application of the non-heatenergy.

Additional Embodiments

In one embodiment, the method includes loading the mold with theparticles (12) and feeding steam to the particles (12) in the mold. Thefeeding of steam heats the particles (12) and can expand thethermoplastic elastomer foam (14). The feeding of steam can also melt orsoften the exterior non-foamed polymer (16) such that the particles (12)fuse, stick, or bond to one another. The method of this disclosure mayinclude one or more steps, components, conditions, or processingparameters as described in US 2013/0291409, which is expresslyincorporated herein in its entirety in various non-limiting embodiments.

In various embodiments, the particles (12) are loaded into the mold withatmospheric pressure and can be later pressurized within the mold. Tothis end, a variety of different methods may be used. For example, suchsteps may be achieved by reducing the volume of the mold. In someembodiments, to this end, a moveable part of the mold is moved such thatthe volume of the mold is reduced. In further embodiments, the mold isdesigned such that the pressure within the mold is locally varied.Alternatively, the particles (12) may be loaded into the mold alreadyunder pressure, e.g. with a locally varying pressure. That way, themanufacturing method may be accelerated.

The pressure to which the particles (12) are compressed in the mold mayinfluence the density and the strength of the eventual article (10). Thediameter of the particles (12) may be reduced by the exerted pressure.For example, with higher pressures, the particles (12) may be compressedand densified more strongly. By reducing the pressure, the particles(12) may re-expand to approximately their original diameters. Theexterior non-foamed polymer (16) may foam or not foam during the processand may collapse or not collapse during the process.

In still other embodiments, the method may include the step of closingthe mold and pre-treating the mold with steam. The method may alsoinclude the step of cooling the mold with water and/or air that are fedthrough the mold. Thus, the article (10) and/or the particles (12) maybe cooled indirectly via the mold. In certain embodiments, the durationof the method is about 3-15 minutes. The duration may alternatively beabout 3-6 minutes for less elaborate methods. Still further, the methodmay have a duration of longer than 15 minutes.

This disclosure also provides the extrudate or the tubular structure(prior to chopping or segmenting) by itself independent of any particlesor any article. Similarly, this disclosure also provides the pluralityof particles by themselves, independent from any extrudate or tubularstructure or article. The extrudate or tubular structure may be any asdescribed above. Similarly, the plurality of particles may be any asdescribed above.

In still other embodiments, the particles are covered by, or coatedwith, a commercially available adhesive (e.g. one or two component) andpressed together in a mold to form a desired article.

This disclosure further provides the article that is further defined asa shoe sole. In various embodiments, the shoe sole includes theparticles that are formed using one or more polyether thermoplasticelastomers. The shoe sole may have one or more dimensions, attributes,or components as described in US 2013/0291409, which is expresslyincorporated herein in its entirety in various non-limiting embodiments.Additionally, the description of softening temperature may bealternatively described as a softening range, as described in U.S. Pat.No. 5,674,600, which is expressly incorporated herein by reference inits entirety in one or more non-limiting embodiments. In variousembodiments, this disclosure provides a capstock (e.g. the polymerdisposed on the exterior surface) that allows for bonding of theparticles at a low temperatures without ruining the rest of thestructure of the particles and/or the article as a whole. For example,these advantages may be observed through one or more physical propertiesdescribed above such as, but not limited to, density and ultimatebreaking strength.

Examples

A series of articles are formed according to this disclosure. Morespecifically, a non-foamed thermoplastic elastomer is provided alongwith an exterior polymer. The thermoplastic elastomer and the exteriorpolymer are co-extruded to form a tubular extrudate wherein thethermoplastic elastomer is foamed during co-extrusion to form athermoplastic elastomer foam and the exterior polymer is disposed on thethermoplastic elastomer foam as an outermost layer of the tubularextrudate. The tubular extrudate is then segmented to form a pluralityof anisotropic tubular particles including the thermoplastic elastomerfoam and the exterior polymer disposed on the thermoplastic elastomerfoam as an outermost layer of the tubular particles. The plurality ofanisotropic tubular particles are then disposed in a mold and heated toform the article. After formation, the articles are evaluated todetermine density.

A first article is formed using Elastollan® 1180A10 as the thermoplasticelastomer (having a Shore hardness of 80A) and Elastollan® 880A13N asthe exterior non-foamed polymer which includes 0.25 weight percent ofbarium titanate as the additive. The thermoplastic elastomer is extrudedand foamed with a combination of blowing agents: Elastollan Konz V2894at 3% loading and Elastollan Konz V2893 at 3% loading. The thermoplasticelastomer has a foamed specific gravity of approximately 0.4 gram/mL.The tubing has an average outer diameter of 0.125 inches. The exteriorpolymer has an average wall thickness of 0.004 inches. The foamedthermoplastic elastomer has an average wall thickness of 0.030 inches.The plurality of anisotropic particles has a loose bulk density of 0.16gram/mL. The plurality of anisotropic particles are exposed to microwaveenergy to selectively heat the non-foamed polymer to its softeningtemperature prior to the thermoplastic elastomer foam reaching itssoftening temperature and form the article such that the plurality ofanisotropic tubular particles are randomly oriented in the article.Various articles are formed having a density from 0.20 to 0.26 gram/mL.

A second article is formed using Elastollan® 1190A10 as thethermoplastic elastomer (having a Shore hardness of 90A) and Elastollan®880A13N as the exterior non-foamed polymer which includes 0.25 weightpercent of barium titanate as the additive. The thermoplastic elastomeris extruded and foamed with a combination of blowing agents: ElastollanKonz V2894 at 3% loading and Elastollan Konz V2893 at 3% loading. Thethermoplastic elastomer has a foamed specific gravity of approximately0.4 gram/mL. The tubing has an average outer diameter of 0.125 inches.The exterior polymer has an average wall thickness of 0.004 inches. Thefoamed thermoplastic elastomer has an average wall thickness of 0.030inches. The plurality of anisotropic particles has a loose bulk densityof 0.16 gram/mL. The plurality of anisotropic particles are exposed tomicrowave energy to selectively heat the non-foamed polymer to itssoftening temperature prior to the thermoplastic elastomer foam reachingits softening temperature and form the article such that the pluralityof anisotropic tubular particles are randomly oriented in the article.Various articles are formed having a density from 0.20 to 0.26 gram/mL.

In various embodiments, the density of the thermoplastic elastomer foamcan be minimized as the performance of the particle may depend on themodulus achieved from the exterior polymer. The lower softening/meltingpoint of the exterior polymer may allow for lower processingtemperatures during molding to avoid permanent distortion of theparticles and subsequent densification of the article. Moreover, thisdisclosure may allow for formation of lower density articles whilemaintaining performance (e.g. energy absorption and return). Lowerdensities may allow the particles to better compete with traditionalthermoset foams commonly seen in furniture cushions, mattresses, andautomotive seating. A thermoplastic elastomer is also considered more“recycle friendly” than a thermoset polymer. This disclosure may alsoenable lower processing temperatures to be used to thermally bond theparticles under pressure without permanently deforming them.

All combinations of the aforementioned embodiments throughout the entiredisclosure are hereby expressly contemplated in one or more non-limitingembodiments even if such a disclosure is not described verbatim in asingle paragraph or section above. In other words, an expresslycontemplated embodiment may include any one or more elements describedabove selected and combined from any portion of the disclosure.

One or more of the values described above may vary by ±5%, ±10%, ±15%,±20%, ±25%, etc. so long as the variance remains within the scope of thedisclosure. Unexpected results may be obtained from each member of aMarkush group independent from all other members. Each member may berelied upon individually and or in combination and provides adequatesupport for specific embodiments within the scope of the appendedclaims. The subject matter of all combinations of independent anddependent claims, both singly and multiply dependent, is hereinexpressly contemplated. The disclosure is illustrative including wordsof description rather than of limitation. Many modifications andvariations of the present disclosure are possible in light of the aboveteachings, and the disclosure may be practiced otherwise than asspecifically described herein.

It is also to be understood that any ranges and subranges relied upon indescribing various embodiments of the present disclosure independentlyand collectively fall within the scope of the appended claims, and areunderstood to describe and contemplate all ranges including whole and/orfractional values therein, even if such values are not expressly writtenherein. One of skill in the art readily recognizes that the enumeratedranges and subranges sufficiently describe and enable variousembodiments of the present disclosure, and such ranges and subranges maybe further delineated into relevant halves, thirds, quarters, fifths,and so on. As just one example, a range “of from 0.1 to 0.9” may befurther delineated into a lower third, i.e. from 0.1 to 0.3, a middlethird, i.e. from 0.4 to 0.6, and an upper third, i.e. from 0.7 to 0.9,which individually and collectively are within the scope of the appendedclaims, and may be relied upon individually and/or collectively andprovide adequate support for specific embodiments within the scope ofthe appended claims. In addition, with respect to the language whichdefines or modifies a range, such as “at least,” “greater than,” “lessthan,” “no more than,” and the like, it is to be understood that suchlanguage includes subranges and/or an upper or lower limit. As anotherexample, a range of “at least 10” inherently includes a subrange of fromat least 10 to 35, a subrange of from at least 10 to 25, a subrange offrom 25 to 35, and so on, and each subrange may be relied uponindividually and/or collectively and provides adequate support forspecific embodiments within the scope of the appended claims. Finally,an individual number within a disclosed range may be relied upon andprovides adequate support for specific embodiments within the scope ofthe appended claims. For example, a range “of from 1 to 9” includesvarious individual integers, such as 3, as well as individual numbersincluding a decimal point (or fraction), such as 4.1, which may berelied upon and provide adequate support for specific embodiments withinthe scope of the appended claims.

1. An article having a density of from 0.03 to 0.45 g/cc and comprisinga plurality of anisotropic tubular particles that are randomly orientedin said article, wherein said tubular particles comprise a thermoplasticelastomer foam and a non-foamed polymer disposed on an exterior surfaceof said thermoplastic elastomer foam as an outermost layer of saidtubular particles, wherein each of said thermoplastic elastomer foam andsaid non-foamed polymer independently has a softening temperaturedetermined according to DIN ISO 306, and wherein said non-foamed polymercomprises an additive that is responsive to non-heat energy toselectively heat said non-foamed polymer to its softening temperatureprior to said thermoplastic elastomer foam reaching its softeningtemperature.
 2. The article of claim 1 wherein said non-heat energy ischosen from microwave energy, radio frequency energy, laser energy,infrared energy, ultraviolet energy, x-ray energy, e-beam energy,electromagnetic energy, magnetic energy, electrical energy, andcombinations thereof.
 3. The article of claim 1 wherein said non-heatenergy is microwave or radio-frequency energy.
 4. The article of claim 1wherein said additive is chosen from barium, titanate, aluminum, carbon,and combinations thereof.
 5. The additive of claim 1 wherein saidadditive is present in an amount of from 0.1 to 10 weight percent basedon a total weight of said non-foamed polymer.
 6. The article of claim 1wherein said thermoplastic elastomer foam and said non-foamed polymerare chemically identical.
 7. The article of claim 1 wherein saidthermoplastic elastomer foam and said non-foamed polymer are chemicallydifferent.
 8. The article of claim 1 wherein said thermoplasticelastomer foam is a thermoplastic polyurethane foam.
 9. The article ofclaim 8 wherein said thermoplastic polyurethane foam is the foamedreaction product of a polyether polyol, an isocyanate component, and achain extender.
 10. The article of claim 8 wherein said thermoplasticpolyurethane foam is the foamed reaction product of a polyester polyol,an isocyanate component, and a chain extender.
 11. The article of claim1 wherein said thermoplastic elastomer foam is formed from athermoplastic polyurethane that has a hardness from 40A to 83D asdetermined using DIN ISO 7619-1.
 12. The article of claim 8 wherein saidthermoplastic polyurethane foam is the foamed reaction product of analiphatic and/or olefinic polyol, an isocyanate component and a chainextender.
 13. The article of claim 1 wherein said thermoplasticelastomer foam is formed from a thermoplastic polyurethane that has ahardness from 80A to 95A as determined using DIN ISO 7619-1.
 14. Thearticle of claim 1 wherein said thermoplastic elastomer foam has adensity of from 0.1 to 0.6 g/cc.
 15. The article of claim 1 having anultimate breaking strength of from 0.1 to 4.0 megapascal as determinedusing ASTM D
 5035. 16. The article of claim 1 wherein said tubularparticles are fused together at a plurality of points.
 17. The articleof claim 1 wherein each of said tubular particles independently has alength from 1 to 30 mm and a diameter from 1 to 30 mm.
 18. The articleof claim 1 that is further defined as a shoe sole, a cushion, a flooringmaterial, or a flooring substrate.
 19. A method of forming an articlehaving a density of from 0.03 to 0.45 g/cc, said method comprising thesteps of: A. providing a thermoplastic elastomer and a non-foamedpolymer each independently having a softening temperature determinedaccording to DIN ISO 306, wherein the polymer comprises an additive thatis responsive to non-heat energy to selectively heat the non-foamedpolymer to its softening temperature prior to the thermoplasticelastomer foam reaching its softening temperature; B. co-extruding thethermoplastic elastomer and the non-foamed polymer to form a tubularextrudate wherein the thermoplastic elastomer is foamed to form athermoplastic elastomer foam during co-extrusion and the non-foamedpolymer is disposed on an exterior surface of the thermoplasticelastomer foam as an outermost layer of the tubular extrudate; C.segmenting the tubular extrudate to form a plurality of anisotropictubular particles comprising the thermoplastic elastomer foam and thenon-foamed polymer disposed on an exterior of the thermoplasticelastomer foam as an outermost layer of the tubular particles; D.disposing the plurality of anisotropic tubular particles in a mold; andE. applying non-heat energy to the plurality of anisotropic tubularparticles to selectively heat the non-foamed polymer to its softeningtemperature prior to the thermoplastic elastomer foam reaching itssoftening temperature and form the article such that the plurality ofanisotropic tubular particles are randomly oriented in the article. 20.The method of claim 19 wherein the non-heat energy is chosen frommicrowave energy, radio frequency energy, laser energy, infrared energy,ultraviolet energy, x-ray energy, e-beam energy, electromagnetic energy,magnetic energy, electrical energy, and combinations thereof.